Chemical Engineering Journal 171 (2011) 734741

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Absorption of carbon dioxide into piperazine activated aqueous

N-methyldiethanolamine
Arunkumar Samanta a , S.S. Bandyopadhyay b,
a
Department of Chemical Engineering, GCET, Vallabh Vidyanagar, Gujarat 388 120, India
b
Separation Science Laboratory, Cryogenic Engineering Centre, IIT Kharagpur, West Bengal 721 302, India

a r t i c l e i n f o a b s t r a c t

Article history: This work presents a theoretical and experimental investigation on the absorption of CO2 into piperazine
Received 31 May 2010 (PZ) activated aqueous N-methyldiethanolamine (MDEA) solvent. A comprehensive mathematical model
Received in revised form 21 January 2011 which is based on Higbies penetration theory has been developed to analyze the experimental data.
Accepted 5 February 2011
The model involving coupled mass transferreaction kineticschemical equilibrium incorporates the
important reversible reactions in the liquid phase. The model is validated with the experimental results of
Keywords:
steady state absorption measurements of CO2 in a 2.81 102 m o.d. stainless steel wetted wall contactor.
CO2 capture
The rates of absorption of CO2 into this solvent have been measured over the CO2 partial pressure range of
Absorption
Modelling
214 kPa and temperature range of 298313 K under atmospheric pressure. The absorption experiments
Kinetics are performed over the MDEA concentration range of 1.892.41 kmol m3 along with PZ concentrations of
MDEA 0.24, 0.60 and 0.95 kmol m3 . The predicted absorption rates and enhancement factors based on the model
Piperazine have been found to be in good agreement with the experimental results, the average absolute deviation
between the model predicted and experimental results being 6.8%. The values of the rate constants, k23
and k25 for the PZ-carbamate and PZ-dicarbamate formation reactions determined in this work have been
found to be about 17,500 m6 kmol2 s1 and 15,500 m6 kmol2 s1 at 298 K, respectively. Good agreement
between the model predicted and experimental results validates the mathematical model developed in
this work to represent CO2 mass transfer in PZ activated aqueous MDEA.
2011 Elsevier B.V. All rights reserved.

1. Introduction equilibrium capacities for CO2 , a higher degradation resistance, and

lower energy requirements for regeneration. In view of this, exten-
Carbon dioxide capture from the ue gas streams of thermal sive research activities are in progress globally to develop efcient
power plants is very important today to mitigate the problem of and economic processes for CO2 capture from the ue gas streams
global warming. The United Nations Intergovernmental Panel on of thermal power plants. Besides CO2 capture from the ue gas
Climate Change (IPCC) identied CO2 capture and storage as one streams of thermal power plants, the removal of CO2 from indus-
of several approaches to address the problem of global warming trial gas streams is an important step in processing sour natural gas,
and climate change [1]. Hence, efcient and less energy intensive renery off-gases, and synthesis gas [24].
capture of CO2 from ue gases with subsequent geological stor- Most frequently, the removal of CO2 from various industrial
age is increasingly being viewed as one of the options for reducing gas streams is done by the regenerative chemical absorption
CO2 emissions. Major challenges for CO2 capture from the ue gas into aqueous solutions of alkanolamines. Commercially available
stream of a fossil fuel red power plant are the large volumet- alkanolamine solvents for these processes are monoethanolamine
ric ow rate of ue gas with large amount of CO2 at low partial (MEA), diethanolamine (DEA), diglycolamine (DGA), diiso-
pressure. The ue gas from a power plant mainly contains of nitro- propanolamine (DIPA), N-methyldiethanolamine (MDEA), and
gen, water vapor and CO2 . For coal based thermal power plants the 2-amino-2-methyl-1-propanol (AMP) [3]. Recently, there is a
ue gas may also contain SO2 and NOx which are known to form growing interest in the use of piperazine (PZ) activated aqueous
heat stable salts with the amines used for CO2 capture leading to MDEA for gas treating processes [512] in order to achieve higher
substantial solvent degradation. Therefore, potential solvents for overall reaction rate for CO2 and reduced regeneration energy
CO2 capture are only those which have high reaction rates, high requirement. PZ is used as an activator in the activated MDEA
process of BASF [5]. Being a cyclic diamine, each mole of PZ can
theoretically absorb two moles of CO2 , and it may favor rapid
Corresponding author. formation of the carbamates. The apparent second-order rate
E-mail address: ssbandyo@hijli.iitkgp.ernet.in (S.S. Bandyopadhyay). constant of PZ has been found to be an order higher than that of the

1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.02.008
 A. Samanta, S.S. Bandyopadhyay / Chemical Engineering Journal 171 (2011) 734741 735

primary amine MEA [9]. While there is extensive published litera- Higbies penetration theory with the assumption that all reactions
ture on the use of primary, secondary and tertiary alkanolamines are reversible. Since liquid bulk concentrations of all species are
and their blends for the removal of CO2 , literature on PZ activated essential for the analysis of mass transfer, a bulk liquid equilib-
MDEA solvent system is very limited. rium model has also been developed to estimate the initial liquid
Xu et al. [7] measured the absorption rate of pure CO2 gas at bulk concentrations of all chemical species. The developed model
atmospheric pressure into aqueous blends of MDEA/PZ using a that comprises sets of partial differential equations coupled with
disk column in the temperature range of 303343 K. The concen- nonlinear algebraic equations is capable of predicting the CO2
tration range of PZ was 0.0140.21 M, which was too low to be absorption rates and enhancement factors in aqueous (MDEA + PZ)
used commercially for CO2 removal processes. Besides, absorption solutions using the relevant physicochemical properties and wet-
measurements were done at high partial pressure of CO2 (pure ted wall contactor hydrodynamics.
CO2 ) leading to almost complete depletion of PZ at the gasliquid
interface. Hence, their results on the kinetics of CO2 PZ appear to 2.1. Reaction scheme and mechanism
be erroneous [13]. Zhang et al. [8] suggested the mechanism of
CO2 absorption into an aqueous solution of MDEA blended with When CO2 is absorbed into an aqueous mixed amine solution
PZ using a disk column with the PZ concentration in the range of of MDEA (R1 R2 R3 N, where, R1 = CH3 and R2 = R3 = C2 H4 OH) and PZ
0.20.6 M. Bishnoi and Rochelle [9] reported CO2 absorption data several reactions may take place. Based on the studies conducted
in 0.6 M PZ in 4.0 M aqueous MDEA solutions at 313 and 343 K by Bishnoi and Rochelle [16] and Kamps et al. [10] for absorption of
using wetted wall contactor. Rate model based on eddy diffusiv- CO2 into aqueous solutions of MDEA and PZ, the following reactions
ity theory was used for prediction of the rate of absorption and are considered for the model development:
enhancement factor. Zhang et al. [14] extended their investigation K ,k
to study the effects of CO2 partial pressure on the absorption of
1 21
CO2 + R1 R2 R3 N + H2 O R1 R2 R3 NH+ + HCO
3 (1)
CO2 into aqueous MDEA/PZ in a laboratory packed column. They K2 ,k22 +
CO2 + PZ + H2 O PZCOO + H3 O (2)
concluded from their results that the absorption rates at elevated K3 ,k23 +
CO2 partial pressures were higher than those predicted from the CO2 + R1 R2 R3 N + PZ PZCOO + R1 R2 R3 NH (3)
model. Recently, Derks [12] studied experimentally the rates of K4 ,k24 +
CO2 + PZCOO + H2 O PZ(COO )2 + H3 O (4)
absorption of CO2 into aqueous solutions containing a mixture of
K5 ,k25 +
4.0 M MDEA and (0.51.0) M PZ in stirred cell contactor at vari- CO2 + R1 R2 R3 N + PZCOO PZ(COO )2 + R1 R2 R3 NH (5)
ous CO2 partial pressures and at 298.15 K. However, the absorption K6 ,k26
CO2 + OH HCO (6)
model proposed by Derks [12] was unable to predict the exper- 3
imental results with reasonable accuracy at high CO2 loadings. K7
Hence, it is evident from the foregoing discussion that in spite of HCO 2
3 + H2 OCO3 + H3 O
+
(7)
great commercial signicance of the PZ activated aqueous MDEA K8
solvents, published literature on the theoretical and experimental PZ + H3 O+ PZH+ + H2 O (8)
investigation on the rates of absorption of CO2 into PZ activated K9
PZCOO + H3 O+ PZH+ COO + H2 O (9)
aqueous MDEA solvent is extremely limited. Moreover, except the
work reported by Samanta [15], there is no literature on the cou- K10
R1 R2 R3 N + H3 O+ R1 R2 R3 NH+ + H2 O (10)
pled mass transferreaction kineticsequilibrium comprehensive
model to represent the absorption of CO2 into aqueous blends of K11
2H2 OH3 O+ + OH (11)
(MDEA + PZ) with various relative compositions of the amines.
This work presents an experimental and theoretical investiga- where Ki is the equilibrium constant for reaction (i) and k2i is the
tion on the absorption of CO2 into PZ activated aqueous MDEA forward rate coefcient for reaction (i). Reactions (1)(6) are con-
solvent. The rates of absorption of CO2 into aqueous solutions of sidered to be reversible with nite reaction rates, whereas reactions
MDEAPZ have been measured in a wetted wall contactor over the (7)(11) are considered to be reversible and instantaneous with
CO2 partial pressure range of 214 kPa and temperature range of respect to mass transfer and at equilibrium, since they involve pro-
298313 K under atmospheric pressure. In view of industrial gas ton transfer only.
treating conditions the absorption experiments are performed over As proposed by Donaldson and Nguyen [17], the reaction mech-
the MDEA concentration range of 1.892.41 kmol m3 (2228 wt%) anism for CO2 with tertiary amines (e.g., MDEA) is a base-catalyzed
along with PZ concentrations of 0.24, 0.60 and 0.95 kmol m3 hydration reaction as shown in the reaction (1). The mechanism
(28 wt%) keeping the total amine concentration in the solution at implies that MDEA does not react directly with CO2 . Versteeg and
30 wt%. Required physicochemical properties, such as density and van Swaaij [18], who studied CO2 absorption into nonaqueous solu-
viscosity of aqueous amine solvents and Henrys constant and dif- tions of MDEA, found that only physical absorption occurs in the
fusivity of CO2 in the solvents have been determined in this work nonaqueous tertiary amine solvent. This supports the validity of
by appropriate experimental methods or estimated from available the reaction (1). The proposed mechanism for the reaction between
literature. A coupled mass transferreaction kineticsequilibrium CO2 and PZ involves the formation of a zwitterion followed by the
model, which is capable of predicting gas absorption rates and deprotonation of zwitterion by a base to produce PZ-carbamate and
enhancement factors for absorption of CO2 into activated amine protonated base [13,1921]. The most important contribution to
solvents has been developed based on Higbies penetration theory. the deprotonation of the zwitterion in an aqueous solution of MDEA
and PZ would come from PZ, MDEA and to a lesser extent from
OH and H2 O. The presence of signicantly more MDEA appears
2. Reaction scheme and mathematical model to catalyze the reaction of CO2 and PZ to form carbamate. In the
case of PZ, formation of zwitterion should be the rate determining
For the rational design and simulation of gas-treating units step, while the deprotonation step involves only a proton transfer
involving blended amine solvents, it is essential to develop mass and is considered to be very fast. In this work, reaction (2) repre-
transfer rate-based models to describe the CO2 mass transfer in sents the reaction between CO2 and PZ for producing carbamate
these solvents. In this section, the diffusion-reaction processes for [13]. The rate constant, k22 , is considered the global rate coef-
CO2 mass transfer in activated MDEA are modeled according to cient for the formation of zwitterion and zwitterion deprotonation
736 A. Samanta, S.S. Bandyopadhyay / Chemical Engineering Journal 171 (2011) 734741

(Eq. (2)). Similarly, the rate constant, k24 , is viewed as the global 2.3. Diffusion-reaction model
rate coefcient for the formation of PZ-dicarbamate, PZ(COO )2 ,
by the reaction (4). Therefore, the proposed reaction scheme does All reactions are treated as reversible reactions. Reactions
not rule out the possible formation of a zwitterion reaction inter- (1)(6) have nite reaction rates which are given by the following
mediate. Besides, two rate constants for reactions (3) and (5) have reaction rate expressions:
been considered here as suggested by Bishnoi and Rochelle [9] for
k21
the absorption of CO2 into (MDEA + PZ + H2 O). R1 = k21 u1 u2 + u3 u4 (24)
K1

2.2. Bulk liquid equilibrium model k22

R2 = k22 u1 u8 + u7 u10 (25)
K2
The liquid bulk concentrations of all chemical species can be
estimated from the initial concentration of MDEA and PZ, the initial k23
R3 = k23 u1 u2 u8 + u3 u10 (26)
CO2 loading, 1 , of the solution and the assumption that all reac- K3
tions are at equilibrium. We have the following twelve equations k24
for twelve liquid bulk concentrations: R4 = k24 u1 u10 + u12 u7 (27)
K4

overall MDEA balance: k25

R5 = k25 u1 u2 u10 + u3 u12 (28)
K5
u02 + u03 = [MDEA]initial (12)
k26
R6 = k26 u1 u5 + u4 (29)
overall PZ balance: K6

u08 + u09 + u010 + u011 + u012 = [PZ]initial (13) The mass transfer model describing the diffusion-reaction pro-
cess consists of following equations:
overall CO2 balance:
  CO2 balance:
u01 + u04 + u06 + u010 + u011 + 2u012 = 1 [MDEA]initial + [PZ]initial

2 u1 
6
(14) u1
= D1 + Ri (30)
t x2
electroneutrality balance: i=1

u03 + u07 + u09 u04 u05 2u06 u010 2u012 = 0 (15) Total carbon (from CO2 ) balance:

u1 u4 u6 u10 u11 u12 2 u1 2 u4

All reactions are in equilibria: + + + + +2 = D1 2
+ D4
t t t t t t x x2
u07 u010 2 u6 2 u10 2 u11 2 u12
K2 = (16) +D6 + D10 + D11 + 2D12 (31)
u01 u08 x2 x2 x2 x2
Total MDEA balance:
u07 u012
K4 = (17)
u01 u010 u2 u3 2 u2 2 u3
+ = D2 + D3 (32)
t t x2 x2
u04
K6 = (18) Total PZ balance:
u01 u05
u8 u9 u10 u11 u12 2 u8 2 u9
+ + + + = D8 + D9
u06 u07 t t t t t x 2 x2
K7 = (19)
u04 2 u10 2 u11 2 u12
+D10 + D11 + D12 (33)
x2 x2 x2
u09
K8 = (20)
u07 u08 Carbamate balance:

u10 u11 2 u10 2 u11

u011 + = D10 + D11 R2 R3 + R4 + R5 (34)
K9 = (21) t t x2 x2
u07 u010
Dicarbamate balance:
u03
K10 = (22) u12 2 u12
u02 u07 = D12 R4 R5 (35)
t x2

K11 = u05 u07 (23) Electroneutrality balance:

where u1 = [CO2 ], u2 = [R1 R2 R3 N], u3 = [R1 R2 R3 NH+ ], u4 = [HCO3 ], u3 u7 u9 u4 u5 u6 u10 u12

+ + 2 2
u5 = [OH ], u6 = [CO3 2 ], u7 = [H3 O+ ], u8 = [PZ], u9 = [PZH+ ], t t t t t t t t
u10 = [PZCOO ], u11 = [PZH+ COO ] and u12 = [PZ (COO )2 ] and 2 u3 2 u7 2 u9 2 u4 2 u5
superscript 0 denotes initial liquid bulk concentration of species i. = D3 2
+ D7 2
+ D9 2
D4 2
D5
x x x x x2
The twelve simultaneous nonlinear algebraic equations (Eqs.
(12)(23)) have been solved using IMSL Math/Library in FORTRAN 2 u6 2 u10 2 u12
2D6 D10 2D12 (36)
90 for the twelve unknowns (u01 , . . . . . . , u012 ) of the liquid bulk con- x2 x2 x2
centrations.
 A. Samanta, S.S. Bandyopadhyay / Chemical Engineering Journal 171 (2011) 734741 737

Table 1
Physicochemical properties aqueous (MDEA + PZ).

Mass % Mass % [MDEA] [PZ] T   103 HCO2 amine a DCO2 amine 109 a
MDEA PZ (kmol m3 ) (kmol m3 ) (K) (kg m3 ) (kg m1 s1 ) (kPa m3 kmol1 ) (m2 s1 )

28 2 2.41 0.24 298 1025.4 3.183 3441 0.84

28 2 2.41 0.24 303 1023.1 2.692 3838 1.04
28 2 2.41 0.24 308 1020.8 2.251 4267 1.16
28 2 2.41 0.24 313 1018.2 1.925 4661 1.30
25 5 2.15 0.60 298 1024.5 3.341 3303 0.70
25 5 2.15 0.60 303 1022.3 2.778 3660 0.88
25 5 2.15 0.60 308 1019.9 2.317 3926 0.94
25 5 2.15 0.60 313 1017.5 1.965 4203 1.09
22 8 1.89 0.95 298 1023.2 3.481 3259 0.62
22 8 1.89 0.95 303 1021.5 2.891 3651 0.74
22 8 1.89 0.95 308 1019.3 2.413 4090 0.85
22 8 1.89 0.95 313 1016.9 2.028 4454 0.95
30 0 0 2.56 313 1019.3 1.843 4254 1.37
a
Samanta et al. [28].

Instantaneous reactions (7)(11) assumed to be at equilibrium where VL is the volumetric liquid ow rate,  is the density of the
are represented by the equilibrium constants using respective liquid,  is the viscosity of the liquid, and dc and h are the outer
species concentrations as follows: diameter and the absorption length, respectively, of the wetted wall
u6 u7 contactor. The time-averaged absorption rate per unit interfacial
K7 = (37) area is obtained as given in Eq. (47).
u4
u9 
K8 = (38) D1 u1 (0, t)
u8 u7 R = dt (47)
 0
x
u11
K9 = (39)
u10 u7 and the enhancement factor, E, for absorption of CO2 is given by Eq.
u3 (48):
K10 = (40)
u2 u7
K11 = u5 u7 (41) R
E= (48)
kL1 (u1 u01 )
Thus, there are twelve partial differential-algebraic equations
which can be solved for the concentration proles of the twelve where kL1 is the liquid-phase mass transfer coefcient dened by
chemical species (u1 , . . . . . . , u12 ) present in the liquid phase of Higbies penetration model.
CO2 (MDEA + PZ + H2 O).

2.3.1. Initial and boundary conditions 2.3.2. Method of solution

At t = 0 (for all x 0) and at x = (for all t 0), the concentration The method-of-lines (MOL) is used to transform each partial dif-
of all chemical species in the liquid are set equal to their equilibrium ferential equation into a set of ordinary differential equations in t
bulk concentrations, i.e., by discretizing the spatial variable x. The resulting system of ordi-
nary differential equations coupled with the nonlinear algebraic
ui = u0i , i = 1, . . . , 12 (42) equations is solved by using the subroutine DDASSL [22] in FOR-
The uxes of the non-volatile components (i.e., for i = 2, 3,. . .,12) at TRAN. The typical number of nodes used in this work is 450 and
gasliquid interface (i.e., at x = 0) are equal to zero, which implies corresponding nodal spacings are of the order 108 m.
following boundary conditions:
ui 2.4. Physicochemical properties and model parameters
= 0 at x = 0 and t > 0 (43)
dx
Knowledge of the physicochemical and transport properties of
For volatile component, CO2 , the mass transfer rate in the gas phase
the alkanolamines and CO2 , e.g., density and viscosity of the aque-
near the gasliquid interface is equal to the mass transfer rate in
ous amine solutions and diffusivity and physical solubility of CO2
the liquid near the interface:
in the aqueous amine solutions were necessary for analyzing the
u1 results of absorption studies using the numerical model devel-
D1 = kg (p1 H1 u1 (0, t)) at x = 0 and t > 0. (44)
dx oped in this work. The densities and viscosities of the PZ activated
For negligible mass transfer resistance in the gas phase, the bound- aqueous MDEA solutions have been measured by standard pro-
ary condition for CO2 at the gasliquid interface (x = 0, t > 0) reduces cedures and described by Samanta and Bandyopadhyay [23] and
to: also presented in Table 1. The solubility and diffusivity of CO2 in
p1 aqueous amine solutions cannot be found out directly because CO2
u1 (0, t) = u1 = . (45) undergoes reaction with the amines. Hence, these properties were
H1
estimated by the N2 O-analogy [2427]. The solubilities of N2 O in
The differential equations are integrated from t = 0 to t = , the con- aqueous (MDEA + PZ) solutions have been measured using an equi-
tact time, using the above initial and boundary conditions. For librium cell. The diffusivities of N2 O in aqueous amine solutions
wetted wall contactor, the contact time  is given by have been measured using the wetted wall column by the volume
   2 1/3 uptake method. The details of the estimation of these properties
2 3 d c
= h (46) are described in Samanta et al. [28]. The physical solubility and dif-
3 g VL
fusivity of CO2 are estimated from measured N2 O solubility and
738 A. Samanta, S.S. Bandyopadhyay / Chemical Engineering Journal 171 (2011) 734741

Table 2
Equilibrium and forward rate constant correlations used for model.

Equilibrium and forward rate Correlation Reference

constant
5615
K2 ln K2 = 29.31 T
Bishnoi [30]
5615
K4 ln K4 = 30.78 T
Bishnoi [30]
2902.4
K7 log10 K7 = 6.498 0.0238 T Danckwerts and Sharma [31]

1 4351
T

K8 ln K8
= 11.91 T
Pagano et al. [32]
13445.9
K11 ln K11 = 132.899 T
22.4773 ln T Posey [33]
7495.441
K6 log10 (K6 K11 ) = 179.648 + 0.019244 T 67.341 log10 T Read [34]

 T

K9 ln K1 = 8.21 5286 Bishnoi [30]

9  T

K10 ln K1 = 9.4165 4234.98 Austgen [35]

10
7

4579
T

k21 k21 = 2.91 10 exp T
Rinker et al. [36]

4
 4

1 
k22 k22 = 5.8 10 exp 3.510
R T
1
298
Samanta and Bandyopadhyay [37]

4
 4

1 
k24 k24 = 5.95 10 exp 3.5510
R T
1
298
Samanta and Bandyopadhyay [37]
2895
k26 log10 k26 = 13.635 T
Pinsent et al. [38]

diffusivity in the blended amine solutions using N2 O analogy as 3.2. Apparatus and procedure
follows (Eqs. (49) and (50)):
  The stainless steel wetted wall contactor (2.81 102 m o.d.)
HCO2 water used for absorption measurements in this study was similar to
HCO2 amine = HN2 Oamine (49)
HN2 Owater the one used by Saha et al. [39]. Absorption measurements were
  done with (30 wt% MDEA), (28 wt% MDEA + 2 wt% PZ), (25 wt%
DCO2 water MDEA + 5 wt% PZ), and (22 wt% MDEA + 8 wt% PZ) over the CO2 par-
DCO2 amine = DN2 Oamine (50)
DN2 Owater tial pressure range of 214 kPa and temperature range of 298313 K
under atmospheric pressure. Appropriate measures, as described
where HN2 Oamine and HN2 Owater are the measured solubil- by Danckwerts [40] have been incorporated in the design to mini-
ity of N2 O in the amine solution and in water, respec- mize errors due to entrance effect, ripples and rigid lm formation.
tively. DN2 Oamine and DN2 Owater are the measured diffusivity The liquid was introduced in the contactor from the overhead
of N2 O in the amine solution and in water, respectively. storage. Flow rates of CO2 , and N2 were controlled by mass ow
HCO2 water and DCO2 water are the measured solubility and diffu- controllers (Sierra Instruments, USA). Two circulator temperature
sivity of CO2 in water. The estimated HCO2 amine and DCO2 amine controllers (JULABO F 32 and FP 55, FRG) were used to control the
values are presented in Table 1. The diffusion coefcients of amine liquid lm and gas phase temperature within 0.2 K of the desired
in solution have been estimated using the diffusion coefcient of level. Besides, the absorption measurements were conducted in an
MDEA, corrected for the molecular weight by multiplying with enclosure where the environment temperature could be controlled
an appropriate factor, e.g., 1.38 for PZ. The diffusion coefcient within about 2 K to ensure that the temperature controllers of the
of MDEA has been calculated from Eq. (51) as given by Snijder experimental set-up for the gas phase and liquid phase temperature
et al. [29]. The diffusion coefcients of the ionic species have been control could efciently control the absorption temperature.
assumed to be equal to that of PZ. It has been observed earlier by Samanta and Bandyopadhyay
2360.7 [37] that for the contactor used for this work the mass transfer
ln DMDEA = 13.088 24.727 105 [MDEA] (51) resistance to CO2 absorption is negligible at a gas ow rate above
T
160 106 m3 s1 under the conditions of CO2 partial pressure
The equilibrium constants are needed to interpret the results range and temperature range as used for this study. However, to
of CO2 absorption measurement into alkanolamines. Values of the ensure elimination of the gas phase resistance a volumetric gas
independent equilibrium constants have been found out using reli- ow rate of 180 106 m3 s1 was maintained throughout all runs
able correlations presented in Table 2 [3035] and the dependent of gas absorption measurement. CO2 diluted with N2 to make the
ones have been estimated by appropriate combination of the inde- required gas phase composition at the inlet was passed through the
pendent equilibrium constants. The correlations for the reaction mixing tube and the coil immersed in the controlled temperature
rate constants are also given in Table 2 [3638]. bath and nally through the saturators immersed in the same bath.
When the desired gas phase temperature was reached, the concen-
3. Experimental tration of CO2 at the inlet was determined using the HORIBA NDIR
on-line CO2 analyzer (Model: VA 3000, HORIBA, Japan) connected
3.1. Materials through its continuous sampling unit (Model: VS 3000, HORIBA,
Japan). The gas, saturated with water vapor at the temperature of
Piperazine (>99% pure) and MDEA (>98% pure) were supplied absorption, was fed to the top of absorption space of the wetted
by E. Merck (Germany) and were used without further purica- wall contactor. The amine solution thermostated at the tempera-
tion. Distilled water degassed by boiling and cooled to ambient ture of absorption was then fed from the overhead storage to the
temperature under vacuum, was used for preparing the amine solu- contactor at the desired ow rate of about 2 106 m3 s1 . Since
tions. Carbon dioxide (>99.9% pure) and nitrogen gas (>99.999% turbulence appears when liquid lm Reynolds number is greater
pure) used for the absorption measurement were obtained from than 250 [40], liquid ow rate for all runs of this work were xed
Chemtron Science Pvt. Ltd. (India). at about 2 106 m3 s1 . With this ow rate the Reynolds num-
 A. Samanta, S.S. Bandyopadhyay / Chemical Engineering Journal 171 (2011) 734741 739

Table 3
Experimental and model predicted results for the absorption of CO2 into aqueous (MDEA + PZ).

[MDEA] [PZ] T p1  kL 105 Experimental results Predicted results

3 3
kmol m kmol m K kPa s R 106 E R 106 E
kmol m2 s1 kmol m2 s1

2.564 0.0 313 5.04 0.35 7.04 1.32 15.8 1.02 12.2
2.564 0.0 313 7.06 0.39 6.68 1.48 13.4 1.23 11.1
2.564 0.0 313 14.24 0.40 6.57 2.40 10.9 2.17 9.9
2.41 0.24 298 4.8 0.53 4.5 6.05 96.5 5.65 90.1
2.41 0.24 303 4.89 0.49 5.17 6.57 99.7 6.07 92.1
2.41 0.24 308 4.95 0.43 5.85 7.16 105.5 6.83 100.6
2.41 0.24 313 4.84 0.42 6.28 7.75 118.8 8.11 124.3
2.41 0.24 313 1.69 0.43 6.18 4.69 209.4 4.51 201.4
2.41 0.24 313 6.67 0.40 6.39 9.30 101.8 9.11 99.7
2.41 0.24 313 13.83 0.43 6.17 16.5 90.1 16.3 88.9
2.15 0.60 298 4.76 0.50 4.22 7.99 131.5 7.45 122.6
2.15 0.60 303 4.83 0.41 5.22 8.87 128.8 8.71 126.4
2.15 0.60 313 4.66 0.39 5.98 10.90 164.5 10.77 162.5
2.15 0.60 313 1.98 0.40 5.90 5.70 204.9 5.15 185.2
2.15 0.60 313 6.97 0.40 5.90 13.50 137.9 14.02 143.2
2.15 0.60 313 13.27 0.40 5.90 23.20 124.5 24.57 131.8
1.89 0.95 298 4.93 0.45 4.19 9.93 164.4 8.80 145.7
1.89 0.95 303 4.71 0.42 4.74 10.20 166.9 9.73 159.2
1.89 0.95 308 4.75 0.42 5.08 11.20 189.9 11.10 188.2
1.89 0.95 313 4.70 0.39 5.57 11.90 202.4 12.72 216.4
1.89 0.95 313 1.87 0.46 5.31 5.86 262.2 5.17 232.1
1.89 0.95 313 6.69 0.43 5.19 15.30 196.4 16.65 213.8
1.89 0.95 313 13.51 0.45 5.13 28.80 185.1 30.09 193.4

ber was about 40. When the system reached the steady state with second amine group of PZ (i.e., reactions (4) and (5)) has not been
respect to the gas and liquid ow rates, gas phase and liquid lm considered in his model. Therefore, both reactions (4) and (5) to
temperatures, and the gas phase concentration of CO2 at the exit form PZ-dicarbamate and equilibrium between PZ-carbamate and
of the contactor, three liquid samples were collected from liquid its protonated species play an important role with increasing CO2
outlet located at the end of the absorption length at an interval loadings for CO2 (MDEA + PZ + H2 O) system. The average absolute
of about one minute. The amount of total CO2 in each loaded liq- deviation (AAD) in this work for the whole partial pressure range
uid sample was determined immediately by acidulating a known of CO2 when reactions (3)(5) are considered is about 6.8%.
volume of the sample in a glass equilibrium cell placed in a ther- Table 3 presents measured and model predicted rates and
mostated bath and measuring the volume of evolved gas following enhancement factors for absorption of CO2 into (MDEA + PZ + H2 O).
the procedure described by Saha et al. [39]. The corresponding rate As shown in Table 3, the addition of small amounts of PZ to
of absorption of CO2 in the alkanolamine solution was determined an aqueous solution of MDEA results in signicant increase in
from the liquid phase CO2 concentration. the rate of absorption and enhancement factor. For instance, at
T = 313 K and CO2 partial pressure of about 5 kPa, the enhance-
4. Results and discussion ment factors for absorption in aqueous solutions of (30 wt%
MDEA), (28 wt% MDEA + 2 wt% PZ), (25 wt% MDEA + 5 wt% PZ), and
Absorption measurements for CO2 into aqueous (MDEA + PZ) at (22 wt% MDEA + 8 wt% PZ) are about 15.8, 118.8, 164.5 and 202.4,
298, 303, 308 and 313 K have been interpreted according to the respectively. So, by replacing 2 wt% MDEA with 2 wt% PZ, the
model developed and described in Section 2 to obtain estimates enhancement factor increased by about 651%. Replacing an addi-
for the rate constants, k23 and k25 . This is achieved by adjusting tional 3 wt% MDEA with PZ increased the enhancement factor by an
the values of rate constants in our mathematical model until the additional 38%. A further replacement of 3 wt% MDEA with an equal
predicted rates of absorption agreed with the experimentally mea- amount of PZ resulted in increasing the enhancement factor by an
sured rates of absorption within 5%. Similar approach was also additional 23.0%. The substantial increase in the enhancement fac-
followed by Rinker [41], Mandal and Bandyopadhyay [42], and tor with the replacement of small amount (2 wt%) of MDEA with PZ
Samanta and Bandyopadhyay [43]. By comparing the model cal- may be due to the increase of PZ-carbamate and PZ-dicarbamate
culated results with the experimental results, it has been observed ions formation catalyzed by higher concentration of MDEA in the
that if reaction (3) is not considered the model under-predicts the solvent. However, as the concentration of PZ is increased further,
rate of absorption by about 28% compared with the experimental say to 8 wt%, in the blend, the change in the enhancement factor
rates for CO2 partial pressure above 5 kPa. From this observation does not follow this trend. This may be due to the reduced diffusiv-
it appears that the role of MDEA in proton transfer is important. ity of CO2 in the solvent with higher concentration of PZ (Table 1).
It is also observed that if reactions (4) and (5) are not consid- Besides, with higher concentration of PZ (and relatively lower con-
ered, the model under predicts the rate of absorption by about centration of MDEA) there is negligible increase in the equilibrium
12% for CO2 partial pressure above 5 kPa. Thus the formation of CO2 capacity of the solvent, which also puts a limit on the rate of CO2
PZ-dicarbamate (reactions (4) and (5)) is also important in the absorption in the solvent. Similar improvement in the specic rate
overall kinetics of CO2 MDEAPZ. Similar view was also made by of absorption and enhancement factor with the addition of small
Derks [12]. The theoretical model developed by Derks [12] pre- amounts of PZ in aqueous AMP has been observed by Samanta and
dicts reasonably their experimentally determined absorption data Bandyopadhyay [43] for absorption of CO2 in aqueous (AMP + PZ).
at very low CO2 loadings without incorporating reactions (4) and The measured and model predicted rates of absorption of CO2 in
(5). However, the same model underpredicts substantially their (MDEA + PZ + H2 O) are compared in the parity plot shown in Fig. 1.
experimentally determined absorption rates at high CO2 loadings. As shown in Fig. 1, the model predicted rates of absorption of CO2
This discrepancy may be due to the fact that the reactivity of the into (MDEA + PZ + H2 O) are in good agreement with the experimen-
740 A. Samanta, S.S. Bandyopadhyay / Chemical Engineering Journal 171 (2011) 734741

Fig. 3. Calculated concentration prole of species in the liquid near the gas-
liquid interface at the end of the absorption length: [MDEA] = 2.15 kmol m3 ,
Fig. 1. Parity plot of model predicted rates and experimental rates of absorption of [PZ] = 0.6 kmol m3 , T = 313 K, p1 = 4.66 kPa and  = 0.39 s.
CO2 into aqueous (MDEA + PZ).

tal results, the AAD between the experimental and model results tematic discrepancy between the k23 values of this study and that
being about 6.8%. of Bishnoi and Rochelle [9] is observed in Fig. 2. This may be due to
The estimated k23 and k25 values obtained for the fact that some of the CO2 absorption studies were conducted
CO2 (MDEA + PZ + H2 O) in this work have been correlated by Bishnoi and Rochelle [9] into loaded solutions and very low par-
according to the following Arrhenius equations. tial pressures. Bishnoi [30] reported that a combined error of 5% in
 1  reading the partial pressure in and out of their contactor can result
4 8.75 104 1 in a 30% error in the ux.
k23 = 1.75 10 exp (52)
R T 298 Typical calculated concentration proles for absorption of CO2
 1  into (25 wt% MDEA + 5 wt% PZ) are shown in Fig. 3. The concentra-
8.75 104 1
k25 = 1.55 104 exp (53) tions of MDEA and PZ near the gasliquid interface are lower by
R T 298 about 1.54% and 36%, respectively, than their liquid bulk concen-
A typical estimate of k23 from this work is plotted in Fig. 2 trations after a gasliquid contact time of about 0.39 s, showing
and compared with the k23 values reported by Bishnoi and substantial depletion of PZ at the gasliquid interface. The deple-
Rochelle [9]. The estimated k23 and k25 values for the reaction tion of more PZ could be due to the fast chemical reaction between
of CO2 with (MDEA + PZ + H2 O) have been found to be about highly reactive PZ and CO2 near the gasliquid interface to form
17,500 m6 kmol2 s1 and 15,500 m6 kmol2 s1 at 298 K, respec- PZ-carbamate and PZ-dicarbamate. Although the change in con-
tively. Bishnoi and Rochelle [9] reported the values of k23 and k25 as centration of MDEA between that in the bulk and at the interface is
14,600 m6 kmol2 s1 and 12,700 m6 kmol2 s1 at 298 K, respec- 1.54% only, this change has also been considered in the model for
tively. Thus, the values of the rate constants k23 and k25 are in good the sake of accuracy of the results, instead of the simplifying con-
agreement with those reported by Bishnoi and Rochelle [9]. A sys- sideration that MDEA concentration remains constant at the bulk
value. Besides, it has been checked that the computational time
and complexity do not reduce substantially by considering MDEA
concentration constant at bulk value.

5. Conclusions

In this work absorption of CO2 into PZ activated aqueous

MDEA solution has been studied over the temperature range
of 298313 K under atmospheric pressure using a wetted wall
model contactor. The CO2 partial pressure was varied in the
range 214 kPa, keeping the total amine concentration at 30 wt%.
The absorption data are interpreted by using a coupled mass
transferkineticsequilibrium mathematical model in which all
reactions are considered reversible.
New kinetic parameters, k23 and k25 for the PZ-monocarbamate
and PZ-dicarbamate formation reactions have been obtained using
the mathematical model and the measured absorption data of this
work. The estimated k23 and k25 values obtained by adjustment
in the model for the reaction of CO2 with (MDEA + PZ + H2 O) in
this work has been found to be about 17,500 m6 kmol2 s1 and
15,500 m6 kmol2 s1 at 298 K, respectively. Bishnoi and Rochelle
Fig. 2. Arrhenius plot for the reaction rate constant, k23 of CO2 (MDEA + PZ + H2 O): [9] reported the values of k23 and k25 as 14,600 m6 kmol2 s1
, this work; , Bishnoi and Rochelle [9]. and 12,700 m6 kmol2 s1 at 298 K, respectively. Thus, the rate
 A. Samanta, S.S. Bandyopadhyay / Chemical Engineering Journal 171 (2011) 734741 741

constants are in good agreement with those reported by Bishnoi [19] M. Caplow, Kinetics of carbamate formation and breakdown, J. Am. Chem. Soc.
and Rochelle [9]. From a comparison of the predicted rates from 90 (1968) 67956803.
[20] P.V. Danckwerts, The reaction of CO2 with ethanolamines, Chem. Eng. Sci. 34
the model developed in this work with the experimental rates (1979) 443446.
of absorption, it has been found that it is important to consider [21] P.W.J. Derks, C. Kleingeld, C. van Aken, J.A. Hogendoorn, G.F. Versteeg, Kinetics
both the PZ-carbamate and PZ-dicarbamate formation reactions of absorption of carbon dioxide in aqueous piperazine solutions, Chem. Eng.
Sci. 61 (2006) 68376854.
for the accuracy in model predicted results. In this work, it has [22] L.R. Petzold, A Description of DASSL: A Differential/Algebraic System Solver in
been found that the addition of small amounts of PZ to an aque- Scientic Computing, North-Holland, Amsterdam, 1983.
ous solution of MDEA signicantly enhances the rate of absorption [23] A. Samanta, S.S. Bandyopadhyay, Density and viscosity of aqueous solutions
of piperazine and (2-amino-2-methyl-1-propanol + piperazine) from 298 to
and enhancement factor. A close agreement between the model
333 K, J. Chem. Eng. Data 51 (2006) 467470.
predicted and experimental results justies the validity of the [24] J.K.A. Clarke, Kinetics of absorption of carbon dioxide in monoethanolamine
mathematical model. solutions at short contact times, Ind. Eng. Chem. Fund. 3 (1964) 239245.
[25] S.S. Laddha, J.M. Diaz, P.V. Danckwerts, The N2 O analogy: the solubilities of CO2
and N2 O in aqueous solutions of organic compounds, Chem. Eng. Sci. 36 (1981)
References 228229.
[26] G.F. Versteeg, W.P.M. van Swaaij, Solubility and diffusivity of acid gases (CO2 ,
[1] IPCC, Carbon dioxide Capture and Storage, Intergovernmental Panel on the Cli- H2 S) in aqueous alkanolamine solutions, J. Chem. Eng. Data 33 (1988) 2934.
mate Change. Prepared by Working Group III of the Intergovernmental Panel [27] A.K. Saha, S.S. Bandyopadhyay, A.K. Biswas, Solubility and diffusivity of N2 O
on the Climate Change, Cambridge University Press, Cambridge, New York, and CO2 in aqueous solutions of 2-amino-2-methyl-1-propanol, J. Chem. Eng.
2005. Data 38 (1993) 7882.
[2] G. Astarita, D.W. Savage, A. Bisio, Gas Treating with Chemical Solvents, John [28] A. Samanta, S. Roy, S.S. Bandyopadhyay, Physical solubility and diffu-
Wiley and Sons, New York, 1983. sivity of N2 O and CO2 in aqueous solutions of piperazine and (N-
[3] A.L. Kohl, R.B. Nielsen, Gas Purication, 5th ed., Gulf Publishing Company, Hous- methyldiethanolamine + piperazine), J. Chem. Eng. Data 52 (2007) 13811385.
ton, TX, 1997. [29] D.E. Snijder, M.J.M. te Riele, G.F. Versteeg, W.P.M. van Swaaij, Diffusion coef-
[4] S.W. Campbell, R.H. Weiland, Modeling of CO2 removal by amine blends. Paper cients of several aqueous alkanolamine solutions, J. Chem. Eng. Data 38 (1993)
Presented at the AIChE Spring National Meeting, Houston, TX, 1989. 475480.
[5] M. Appl, U. Wagner, H.J. Henrici, K. Kuessner, F. Volkamer, N. Ernst, Removal of [30] S. Bishnoi, CO2 absorption and solution equilibrium in piperazine activated
CO2 and/or H2 S and/or COS from gases containing these constituents, US Patent methyldiethanolamine, PhD thesis, The University of Texas at Austin, USA,
4,336,233, 1982. 2000.
[6] R.E. Meissner, A low energy process for purifying natural gas, in: Proceedings of [31] P.V. Danckwerts, M.M. Sharma, The absorption of carbon dioxide into aqueous
the 1983 Gas Conditioning Conference, University of Oklahoma, Norman, 1983. solutions of alkalis and amines (with some notes on hydrogen sulphide and
[7] G.-W. Xu, C.-F. Zhang, S.-J. Qin, Y.-W. Wang, Kinetics study on absorption of car- carbonyl sulphide), Chem. Eng. J. 10 (1966) CE244CE280.
bon dioxide into solutions of activated methyldiethanolamine, Ind. Eng. Chem. [32] J.M. Pagano, D.E. Goldberg, W.C. Fernelius, A thermodynamic study of
Res. 31 (1992) 921927. homopiperazine, piperazine, and N-(2-aminoethyl)-piperazine and their com-
[8] X. Zhang, C.-F. Zhang, S.-J. Qin, Z.-S. Zheng, A kinetics study on the absorption plexes with copper(II) ion, J. Phys. Chem. 65 (1961) 10621064.
of carbon dioxide into a mixed aqueous solution of methyldiethanolamine and [33] M.L. Posey, Thermodynamic model for acid gas loaded aqueous alkanolamine
piperazine, Ind. Eng. Chem. Res. 40 (2001) 37853791. solutions, PhD thesis, The University of Texas at Austin, USA, 1996.
[9] S. Bishnoi, G.T. Rochelle, Absorption of carbon dioxide in aqueous piper- [34] A.J. Read, The rst ionization constant of carbonic acid from 25 to 250 C and
azine/methyldiethanolamine, AIChE J. 48 (2002) 27882799. to 2000 bar, J. Solution Chem. 4 (1975) 5370.
[10] P.-S. Kamps A, J. Xia, G. Maurer, Solubility of CO2 in (H2 O + piperazine) and in [35] D.M. Austgen, A model of vaporliquid equilibria for acid
(H2 O + MDEA + piperazine), AIChE J. 49 (2003) 26622670. gasalkanolaminewater systems, PhD thesis, The University of Texas at
[11] B.S. Ali, M.K. Aroua, Effect of piperazine on CO2 loading in aqueous solutions of Austin, USA, 1989.
MDEA at low pressure, Int. J. Thermophys. 25 (2004) 18631870. [36] E.B. Rinker, S.S. Ashour, O.C. Sandall, Kinetics and modeling of carbon dioxide
[12] P.W.J. Derks, Carbon dioxide absorption in piperazine activated N- absorption into aqueous solutions of N-methyldiethanolamine, Chem. Eng. Sci.
methyldiethanolamine, PhD thesis, University of Twente, The Netherlands, 50 (1995) 755768.
2006. [37] A. Samanta, S.S. Bandyopadhyay, Kinetics and modeling of carbon dioxide
[13] S. Bishnoi, G.T. Rochelle, Absorption of carbon dioxide into aqueous piper- adsorption into aqueous solutions of piperazine, Chem. Eng. Sci. 62 (2007)
azine: reaction kinetics, mass transfer and solubility, Chem. Eng. Sci. 55 (2000) 73127319.
55315543. [38] B.R.W. Pinsent, L. Pearson, F.J.W. Roughton, The kinetics of combination of
[14] X. Zhang, J. Wang, C.-F. Zhang, Y.-H. Yang, J.-J. Xu, Absorption rate into a MDEA carbon dioxide with hydroxide ions, Trans. Faraday Soc. 52 (1956) 15121520.
aqueous solution blended with piperazine under a high CO2 partial pressure, [39] A.K. Saha, S.S. Bandyopadhyay, A.K. Biswas, Kinetics of absorption of CO2 into
Ind. Eng. Chem. Res. 42 (2003) 118122. aqueous solutions of 2-amino-2-methyl-1-propanol, Chem. Eng. Sci. 50 (1995)
[15] A. Samanta, Absorption of carbon dioxide into piperazine activated alka- 35873598.
nolamines, PhD thesis, Indian Institute of Technology Kharagpur, India, 2008. [40] P.V. Danckwerts, GasLiquid Reactions, McGraw-Hill, New York, 1970.
[16] S. Bishnoi, G.T. Rochelle, Thermodynamics of piper- [41] E.B. Rinker, Acid gas treating with blended alkanolamines, PhD thesis, Univer-
azine/methyldiethanolamine/water/carbon dioxide, Ind. Eng. Chem. Res. sity of California, Santa Barbara, USA, 1997.
41 (2002) 604612. [42] B.P. Mandal, S.S. Bandyopadhyay, Absorption of carbon dioxide into aqueous
[17] T.L. Donaldson, Y.N. Nguyen, Carbon dioxide reaction kinetics and transport in blends of 2-amino-2-methyl-1-propanol and monoethanolamine, Chem. Eng.
aqueous amine membranes, Ind. Eng. Chem. Fund. 19 (1980) 260266. Sci. 61 (2006) 54405447.
[18] G.F. Versteeg, W.P.M. van Swaaij, On the kinetics between CO2 and alka- [43] A. Samanta, S.S. Bandyopadhyay, Absorption of carbon dioxide into aqueous
nolamines both in aqueous and nonaqueous solutions II. Tertiary amines, solutions of piperazine activated 2-amino-2-methyl-1-propanol, Chem. Eng.
Chem. Eng. Sci. 43 (1988) 587591. Sci. 64 (2009) 11851194.